# US 4,400,255 A · Control of electron bombardment of the exhaust oxygen sensor during electrode sputtering > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 4,400,255 A - Document ID: US4400255A - Status: Granted - Kind: A - Application number: 06/278,049 - Filed: 1981-06-29 - Granted: 1983-08-23 - Earliest claimed: 1981-06-29 - Assignees: General Motors Corporation - Inventors: Howard D. Kisner - Web page: https://patentgrep.com/patent/US4400255A ## CPC - G01N 27/4075: {Composition or fabrication of the electrodes and coatings thereon, e.g. catalysts} - C04B 41/5122: {Pd or Pt} - C04B 41/88: Metals - C23C 14/34: Sputtering - G01N: INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES (measuring or testing apparatus or processes other than immunoassay, involving enzymes or microorganisms C12M, C12Q) - C04B: LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE {(roofing granules E04D7/005)}; CERAMICS (devitrified glass-ceramics C03C10/00); REFRACTORIES; TREATMENT OF NATURAL STONE - C23C: COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL (making metal-coated products by extrusion B21C23/22; covering with metal by connecting pre-existing layers to articles, see the relevant places, e.g. B21D39/00, B23K; metallising of glass C03C; metallising mortars, concrete, artificial stone, ceramics or natural stone C04B41/00; enamelling of, or applying a vitreous layer to, metals C23D; treating metal surfaces or coating of metals by electrolysis or electrophoresis C25D; single-crystal film growth C30B; by metallising textiles D06M11/83; decorating textiles by locally metallising D06Q1/04) ## Abstract A method of sputtering a platinum exhaust gas electrode onto a vitrified zirconia thimble for an electrochemical-type exhaust gas oxygen sensor. High yields of sensors having fast response times as formed are consistently produced. The exhaust gas outer electrode is sputtered onto the thimble after first forming an inner electrode, using a rate that significantly heats the thimble. The first electrode is maintained electrically isolated from the exhaust electrode during sputtering, and is maintained at a different electrical potential. ## Claims ### Claim 1 In a method of sputtering an exhaust electrode onto a given surface of a zirconia solid electrolyte exhaust gas oxygen sensor body, opposite from a surface on said body having a previously formed reference electrode, the improvement of: providing a low resistance electrical path between the reference electrode and a sputtering anode; sputtering an exhaust electrode onto said body while it is electrically conductive at a pressure of about 10-20 millitorr, a target-body minimum spacing of at least about 3.0 cm, and at a sputtering power of about 13-22 watts/cm.sup.2 of target area used; heating said sensor body to make it significantly electrically conductive; maintaining the exhaust electrode electrically isolated from said reference electrode during said sputtering, so as to maintain a voltage difference between said surfaces during sputtering that enhances sensor rich-to-lean response time; and terminating said sputtering of said exhaust electrode onto said given surface before sensor lean voltages and lean-to-rich response times are adversely affected. ### Claim 2 In a method of sputtering an exhaust electrode onto a given surface of a zirconia solid electrolyte exhaust gas oxygen sensor body, opposite from a surface on said body having a previously formed reference electrode, the improvement of: providing a low resistance electrical path between the reference electrode and a sputtering anode; sputtering the exhaust electrode onto said given surface at a rate sufficient to heat said sensor body and thereby make it significantly electrically conductive; maintaining the exhaust electrode electrically isolated from said reference electrode during said sputtering, so as to maintain a voltage difference between said surfaces during sputtering that electrochemically reduces zirconia to free zirconium adjacent said given surface and oxidizes any free zirconium at said opposite surface, effective to enhance sensor rich-to-lean response time; and terminating said sputtering of said exhaust electrode onto said given surface before apparent zirconia reduction progresses from said given surface to said opposite surface, and adversely affects sensor lean voltages and lean-to-rich response times. ### Claim 3 In a method of sputtering an exhaust electrode onto an outer surface of a hollow thimble zirconia for an exhaust gas oxygen sensor after an inner electrode has been previously formed inside the thimble, the improvement of: providing a low resistance electrical path between the inner electrode and a sputtering anode; sputtering the exhaust electrode onto said given surface in a nitrogen atmosphere containing 30-50 percent by volume argon at a pressure of about 10-20 millitorr, using a minimum thimble-to-target spacing of about 3.0 cm and a sputtering power of about 13-22 watts/cm.sup.2 of target area used, so as to heat the thimble and make it significantly electrically conductive; masking a portion of the thimble to maintain the outer surface of the thimble from electrically contacting the inner electrode during sputtering, so as to maintain a voltage difference between the outer surface and the inner electrode during sputtering that enhances sensor rich-to-lean response time; and terminating the sputtering before sensor lean voltages and lean-to-rich response times are adversely affected. ### Claim 4 In a method of sputtering an exhaust electrode onto an outer surface of a hollow zirconia thimble for an exhaust gas oxygen sensor after a reference electrode has been previously formed on its hollow interior, the improvement of: providing a low resistance electrical path between the reference electrode and a sputtering anode; sputtering the exhaust electrode onto said given surface in an atmosphere consisting essentially of about 50-70 percent by volume of at least one gas selected from the group consisting of oxygen and nitrogen, and the balance an inert gas at a pressure of about 10-20 millitorr using a minimum thimble-to-target spacing of about 3.0 cm and a sputtering power sufficient to heat said sensor body and thereby make it significantly electrically conductive; maintaining the exhaust electrode electrically isolated from said reference electrode during said sputtering, so as to maintain a voltage difference between said surfaces during sputtering that electrochemically reduces zirconia to free zirconium adjacent said given surface and oxidizes any free zirconium at said opposite surface, effective to enhance sensor rich-to-lean response time; and terminating said sputtering of said exhaust electrode onto said given surface before apparent zirconia reduction progresses from said given surface to said opposite surface, and adversely affects sensor lean voltages and lean-to-rich response times.